Survey of long d10-d10 metallophilic contacts in four-membered rings of Ag(I) and Au(I) supported by carbene-pyrazole mixed ligands.

The interesting case of long intramolecular d(10)-d(10) contacts has been studied through Ag(4)L(2) and Au(4)L(2) (L = 3,5-bis((N-methylimidazolyl)methyl)pyrazole) systems, showing interesting features gained by analysis of the electronic structure and the overall shielding tensor in the molecular domain, in terms of its components. The long intramolecular closed-shell separations are attributed to the population of the bonding, nonbonding, and antibonding combinations of the ns atomic shells in the M(4) core, contrasting with that observed in systems with shorter d(10)-d(10) distances. This point allows to concludeb that separations shorter then the sum of the van der Waals radii (3.4 Å for Ag-Ag, and 3.2 Å for Au-Au) of the nucleus involved requires a net bonding population between ns and np atomic shells of the d(10) closed-shell centers. Moreover, Au(4)L(2) exhibits an increased covalency observed for the enhanced charge-donation due to the stabilization of the ns and destabilization of the (n - 1)d driven by the relativistic effects. The magnetic response denotes a slight interaction between the closed-shell centers at distances in the range of their sum of van der Waals radii because the observed remote effect (or anisotropic effect) caused by each d(10) nucleus does not influence considerably the neighbor center. The analysis of δ in terms of its components allows to conclude that the Au(4)L(2) system exhibits an increased magnetic response due to the increase in the number of the inner-electrons in comparison to Ag(4)L(2).